Acrylic modifiers for polycarbonamides

ABSTRACT

An impact resistant nitrogenous polymer comprises a multiphase amine-reactive moiety-containing polymer grafted to a polycarbonamide containing recurring amide linkages as an integral part of the polymer chain; the grafting, by reaction of an amine-reactive moiety of the polymer with an amine end group of the polycarbonamide. Preferably the amine-reactive moietycontaining polymer is a multiphase carboxylic acid-containing polymer comprising (A) a first elastomer phase that is preferably polymerized from monomers comprising; 50 to 99.9 parts by weight alkyl acrylate wherein the alkyl group contains one to 15 carbon atoms, butadiene or substituted butadiene; 0 to 40 parts by weight of other ethylenically unsaturated monomers; 0 to 5 parts by weight of a polyethylenically unsaturated crosslinking monomer; and 0 to 5 parts by weight of a graft-linking monomer; and (B) a final rigid thermoplastic stage containing aminereactive carboxylic acid groups and polymerized from monomers containing; 1 to 50 parts by weight of a copolymerizable carboxylic acid; 50 to 99 parts by weight of a member selected from the group consisting of alkyl methacrylates, styrenes, acrylonitrile methacrylonitrile and olefins that, when homopolymerized, form polymers having a heat distortion temperature greater than about 20* C.; 0 to 49 parts by weight of another acrylic monomer; and 0 to 40 parts of another copolymerizable ethylenically unsaturated monomer. The impact resistance nitrogenous polymer is characterized by superior hot strength that renders the polymer extrudable, blow moldable and injection moldable.

ilited States Patent Owens et a1.

[72] Inventors: Frederick H. Owens, Willingboro, N,.I.;

James S. CIovis,'Wan'ninster, Pa.

[73] Assignee: Rohm and Haas Company, Philadelphia,

[22] Filed: Sept. 10, 1970 [2]] Appl. No.: 71,228 Y [51] Int. Cl ..C08g41/04 [58] Field of Search ..260/857 G, 857 D, 857 U [56] ReferencesCited UNITED STATES PATENTS 3,236,914 2/1966 Murdoch ..260/857 U3,099,631 7/1963 Tanner..... 260/857 G 3,297,471 1/1967 Traumann 260/857G 3,337,648 8/1967 Aelien ...260/857 G 3,496,249 2/1970 Hitzler..260/857 U FOREIGN PATENTS OR APPLICATIONS 740,501 8/1966 Canada..260/857 L 6,705,238 6/1967 Netherlands ..260/857 L 51 June 6, 19726,705,239 6/1967 Netherlands ..260/857L Primary Examiner-Paul LiebermanAttorneyPhilip D. Freedman and George W. F. Simmons [5 7] ABSTRACT Animpact resistant nitrogenous polymer comprises a multiphaseamine-reactive moiety-containing polymer grafted to a polycarbonamidecontaining recurring amide linkages as an integral part of the polymerchain; the grafting, by reaction of an amine-reactive moiety of thepolymer with an amine end group of the polycarbonamide. Preferably theamine-reactive moiety-containing polymer is a multiphase carboxylicacidcontaining polymer comprising (A) a first elastomer phase that ispreferably polymerized from monomers comprising; 50 to 99.9 parts byweight alkyl acrylate wherein the alkyl group contains one to 15 carbonatoms, butadiene or substituted butadiene; 0 to 40 parts by weight ofother ethylenically unsaturated monomers; 0 to 5 parts by weight of apolyethylenically unsaturated crosslinking monomer; and 0 to 5 parts byweight of a graft-linking monomer; and (B) a final rigid thermoplasticstage containing amine-reactive carboxylic acid groups and polymerizedfrom monomers containing; I to 50 parts by weight of a copolymerizablecarboxylic acid; 50 to 99 parts by weight of a member selected from thegroup consisting of alkyl methacrylates, styrenes, acrylonitrilemethacrylonitrile and olefins that, when homopolymerized, form polymershaving a heat distortion temperature greater than about 20 C.; 0 to 49parts by weight of another acrylic monomer; and 0 to 40 parts of anothercopolymerizable ethylenically unsaturated monomer. The impact resistancenitrogenous polymer is characterized by superior hot strength thatrenders the polymer extrudable, blow moldable and injection moldable.

12 Claims, N0 Drawings ACRYLIC MODIFIERS FOR POLYCARBONAMIDES Thisinvention relates to modified polycarbonarnide compositions of improvedproperties. U.S. Pats. Nos. 3,099,631, Tanner, July 30, 1963, and3,394,985, Froehlich, July 30, I968, disclose a nitrogenous polymercontaining carboxylic acid groups within the polymer chain, bonded bycarbon-tocarbon linkages to a catenarian carbon, Le. a noncarboxyliccarbon attached to a nitrogen, and the acid groups so linked being atleast one carbon atom removed from the catenarian carbon. The carboxylicacid groups are used in the form of their salts. The resulting polymersare used in shaped articles particularly fibers characterized byimproved melt resistance, low static propensity and improved wet creaserecovery. U.S. Pat. No. 3,297,471, Traumann, Jan. 10, 1967, shows shapedstructures, particularly yarns fibers, fabrics, films, flakes or thelike, formed by penetrating a polyamide with a polymerizable acid vinylcompound and polymerizing the compound to the polyamide by reaction ofthe vinyl group. The salt of the acid group of the compound is thenformed and the resulting composition used in applications where thermaland static properties are of importance. I

In the resent invention, a polycarbonarnide is modified by a multistage,amine-reactive moiety-containing polymer to render the polycarbonarnideextrudable, blow moldable and injection moldable and otherwise amenableto the application of forming processes. Furthermore, the modifiedcarbonamides of this invention are characterized by increased impactstrength and by modulus values essentially equal to or better than theunmodified polycarbonarnide. The advantageous improved properties of themodified polycarbonarnide are obtained without significant affect onother desirable properties of the unmodified polycarbonarnide such assolvent resistance and vapor barrier properties.

In one embodiment, the present invention relates to the multiphaseamine-reactive moiety-containing modifier itself as a novel compositionof matter. The modifier is a multiphase elastomer-based interpolymer inwhich theouter rigid phase contains amine-reactive moieties, preferablyuncombined carboxylic acid groups, that can be reacted with the amineend groups of the polycarbonarnide. The modifier comprises a first phaseelastomeric polymer selected from the group consisting of thehomopolymers and copolymers of an alkyl acrylate wherein the alkyl groupcontains one to 15 carbon atoms, butadiene, substituted butadiene,urethanes, ethers, esters, and ethylene; and a final rigid thermoplasticpolymeric phase containing amine-reactive moieties. Preferably themodifier comprises: (A) a first elastomer phase that is preferablypolymerized from monomers comprising; 50 to 99.9 parts by weight alkylacrylate wherein the alkyl group contains one to 15 carbon atoms,butadiene or substituted butadiene; to 40 parts by weight of otherethylenically unsaturated monomers; 0 to parts by weight of apolyethylenically unsaturated crosslinking monomer; and 0 to 5 parts byweight of a graft-linking monomer; and (B) a final rigid phasethermoplastic stage containing amine-reactive moieties, preferablecarboxylic acid groups, and polymerized from monomers comprising; 1 to50 parts by weight of a copolymerizable amine-reactive moiety-containingmonomer, preferably a copolymerizable carboxylic acid; 50 to 99 parts byweight of a member selected from the group consisting of alkylmethacrylates, styrenes, acrylonitrile, methacrylonitrile and olefinsthat, when homopolymerized, form polymers having a heat distortiontemperature grater than about C.; 0 to 49 parts by weight of anotheracrylic monomer; and 0 to parts of another copolymerizable ethylenicallyunsaturated monomer.

The reactive groups of the modifier are reacted with the amine endgroups of the polycarbonamide to form a grafted modifier-polycarbonamidecontaining recurring amide linkages as an integral part of the polymerchain; the grafting by reaction of a reactive group, preferably an acidgroup of the modifier, with an amine end group of the polycarbonamide.The preferred modifier content based on the total weight of the modifiedpolymer is 2.5 to 30 percent. Most preferred is '4 to 15 percent.

The present invention also relates to a process for making the modifiedpolycarbonarnide comprising forming a first elastomeric phase of apolymer selected from the group consisting of the homopolymers andcopolymers of an alkyl acrylate wherein the alkyl group contains one to15 carbon atoms, butadiene, substituted butadiene, urethane, ethers,esters, and ethylene; forming an amine-reactive moiety-containing finalrigid thennoplastic phase in the presence of a product containing thefirst elastomeric phase; and reacting a reactive moiety of the resultingpolymer with an amine end group of a polycarbonarnide polymer containingrecurring amide linkages as an integral part of the polymer chain toform a modified interpolymer of improved impact strength. Preferably theprocess comprises: (A) forming a first elastomeric phase bypolymerization of a monomer charge of 50 to 99.9 parts by weight alkylacrylate wherein the alkyl group contains one to 15 carbon atoms,butadiene or substituted butadiene; O to 40 parts by weight of otherethylenically unsaturated monomers; 0 to 5 parts by weight of apolyunsaturated crosslinking monomer; and 0 to 5 parts by weight of agraft-linking monomer; (B) polymerizing in the presence of a productcontaining the elastomeric phase formed in (A), a monomer charge of 1 to50 parts by weight of a copolymerizable amine-reactive moiety-containingmonomer, preferably a copolymerizable carboxylic acid; 50 to 99 parts byweight of a member selected from the group consisting of alkylmethacrylates, styrenes,- acrylonitrile, methacrylonitrile and olefinsthat, when homopolymerized, form polymers having a heat distortiontemperature greater than about 20 C.; 0 to 49 parts by weight of anotheracrylic monomer; and O to 40 parts of another copolymerizableethylenically unsaturated monomer to form a multiphase carb'oxylicacid-containing polymer; and (C) reacting a copolymerizableamine-reactive moiety of the polymer product of (A) and (B) with anamine end group of a polycarbonarnide polymer containing recurring amidelinkages as an integral part of the polymer chain to form a modifiedpolymerpolycarbonamide of improved impact strength.

The polycarbonamides suitable in the present invention include thosethat are amine-terminated and are capable of reacting with thecarboxylic acid-containing modifiers at this termination. Examples ofsuitable polycarbonamides are those prepared from polymerizablemonoamino monocarboxylic acids or their amide-forming derivatives, orfrom suitable diamine and suitable dicarboxylic acids or fromamide-forming derivatives of these compounds. The preferred polyamidesare those wherein the intracarbonamide linkages are other thanexclusively aromatic, i.e., there is at least 1 aliphatic HCR group ineach repeating unit of the polymer molecule. The"R- group may behydrogen, halogen, monovalent organic radical, alkylene or the like.Typical of such polyamides are those formed from an aliphatic diamineand an aliphatic acid containing the repeating unit v -XZYZ wherein X-and -Y represent divalent aliphatic or cycle-aliphatic groups and --Z-represents the linkage. Polyhexamethyleneadiparnide and polycaproamide(i.e., 66" and 66" nylons) are typical. Other suitable polyamides arethose having the repeating structure A-Z--X- 2 where -A- is a divalentaromatic radical and -X- and -Z- are as previously defined.Polyhexamethylene terephthalamide is illustrative of such polymers.Additionally polyamides having repeating units such as .-A-ZBZ andX-Z-BZ-- wherein B is divalent alkaryl (such as xylene may be used.Another class of suitable polyamides containing other than aromaticintracarbonamide repeating units are those prepared from piperazine,such as those from piperazine and adipic acid, piperazine andterephthalic acid, and the like. Copolyamides, condensation copolymerswherein the amide linkage is the predominant linkage and polyamidemixtures are also useful. in one aspect of the present invention thepolycarbonamide is "waste" or scrap" nylon flock.

The acrylic modifier of this invention is an elastomer-based compositeinterpolymer material having a first phase of an elastomer andsubsequent phases which are, at least in part, chemically linked to theelastomer core; these subsequent phases may be elastomeric or rigidthermoplastic or a combination of the two; but the final phase is arigid thermoplastic containing copolymerized acid.

The composite interpolymer material is ordinarily and preferablyprepared by emulsion polymerization of the elastomer as a discrete phasefrom a monomer mix of at least about 50 weight percent alkyl and/oraralkyl acrylate, butadiene or substituted butadiene and one or more ofpolyethenically unsaturated crosslinking monomers and graftlinkingmonomers. The elastomer may also be a polyurethane, polyether,polyethylene and other elastomer well known in the art which can bedispersed in a medium such that subsequent phases may be added.

Upon completion of the polymerization of the elastomeric phase, i.e.,substantial exhaustion of the monomers in the initial polymerizationmix, the subsequent phases are then added in such a fashion thatsubstantially all the subsequent stages are formed at the surface of theprevious stage. The attachment of the subsequent stages to theelastomeric phase may be physical or chemical and includes graftcopolymerization.

Preferred are those elastomers which have a glass temperature less than25 C. More preferred are those elastomers having a glass temperatureless than -25 C. In all cases these glass temperatures refer to theelastomeric portion of the modifier only and do not include anysubsequent phases or other polymers attached physically or chemicallyonto or into the particles of the elastomer.

The elastomers of this invention include acrylic interpolymerscomprising 50 to 99.9 parts by weight alkyl acrylate monomers, whereinthe alkyl group contains 1 to 15 carbon atoms, preferably one to eightand most preferably two to eight carbon atoms, to 40 parts by weight ofother ethylenically unsaturated monomers, 0.1 to parts by weight of atleast one polyunsaturated crosslinking monomer, and 0 to 5 parts byweight of a graft-linking monomer. Preferred are those acrylicelastomers wherein the interpolymer comprises 50 to 90 parts by weightalkyl acrylate monomers, wherein the alkyl group contains one to eightcarbon atoms, 0 to parts by weight other acrylic monomers, 5 to 20 partsby weight other ethylenically unsaturated monomers, as defined below,0.1 to 1.0 parts by weight of at least one polyethylenically unsaturatedcrosslinking monomer unit, and 0.1 to 1.0 parts by weight ofgraft-linking monomer. Other acrylic monomers including aralkyl estersof acrylic acid wherein the cyclic portion contains five, six, or sevencarbon atoms with or without an additional alkyl bridge, and the alkylportion of the aralkyl group contains up to 15 carbon atoms may also beused; substitued acrylates or methacrylates including alkylthioalkylacrylates such as ethyl thioethyl acrylate, and the like, alkoxyalkylacrylates such as methoxyethyl acrylate, and the like, can also be used.Also included in this group are hydroxy alkyl, haloalkyl, cyanoalkyl,nitroalkyl, and the like, acrylates and methacrylates, acrylamide,methacrylamide and alkyl acrylamides and methacrylamides.

Suitable other ethylenically unsaturated monomers include styrene,a-methylstyrene, vinyl and vinylidene halides, vinyl ethers, amides,esters, and the like.

The acrylic elastomers include polyfunctional unsatu-rated monomerscapable of cross-linking the elastomer, such as polyethylenicallyunsaturated monomers like polyacrylates and poiymethacrylates, andmonomers capable of ionic and coordinate crosslinking such as acidgroups and organic and inorganic bases and other electron donatinggroups coordinating with suitable electrophilic agents. The cross-linkedelastomers are referred to as gelled interpolymers to describe thatphysical characteristic of the polymers. The polyethylenicallyunsaturated monomers include polyacrylic and polymethacrylic esters ofpolyols such as butylene diacrylate and dimethacrylate,trimethylolpropane trimethacrylate, and the like, diand trivinylbenzene, vinyl acrylate and methacrylate and other cross-linkingmonomers.

The graft-linking monomers contemplated in the present invention aresimilar to the cross-linking monomers hereinbefore described, but wherethe cross-linking monomers, as that term is commonly employed, and as itis utilized herein, have a plurality of addition polymerizableunsaturated groups, each of which participate in the polymerizationreaction at about the same rate as one another and as the primarymonomers, i.e., the alkyl acrylate monomers, the other acrylic monomers,and the reactive other monomers, the graft-linking monomers in thepresent invention are compounds having two or more additionpolymerizable unsaturated reactive groups which participate in thepolymerization reaction at substantially different rates. It ispreferred to include compounds where at least one reactive grouppolymerizes at about the same rate, or slightly slower than the othermonomers, while the remaining reactive group or groups polymerize at asubstantially different, e.g., slower, rate. The differentialpolymerization rates result in a residual level of unsaturation in theelastomeric phase, particularly during the latter stages ofpolymerization and, consequently, at or near the surface of theelastomer particles. When the rigid thermoplastic phase is subsequenlypolymerized at the surface of the elastomer, the residual unsaturatedadditional polymerizable reactive groups contributed by thegraft-linking monomer participate in the subsequent reaction so that atleast a portion of the following stage or stages particularly the rigidphase is chemically attached to the surface of the elastomer.

The compounds particularly preferred for use as graft-linking monomersin the present invention are allyl methacrylate and allyl acrylate.Other compounds suitable for use as graftlinking monomers in the presentinvention include, by way of example, allyl, methallyl, and crotylesters of acrylic acid, methacrylic acid, maleic acid (monoanddiesters); fumaric acid (monoand diesters) and itaconic acid (monoanddiesters); allyl, methallyl and crotyl vinyl ether; allyl, methallyl,and crotyl vinyl thioether; N-allyl, methallyl or crotyl maleimide;vinyl esters of 3-butenoic and 4-pentenoic acids; triallyl cyanurate;o-allyl, methallyl or crotyl, o-alikyl, aryl, alkaryl or aralkylP-vinyl, -allyl, or-methallyl phosphonate, triallyl, trimethallyl ortricrotyl phosphate; O-vinyl, 0,0-diallyl, dimethallyl or dicrotylphosphate, cycloalkenyl esters of acrylic acid, meth-acrylic acid,maleic acid (monoand diesters), fumaric acid (monoand diesters),itaconic acid (monoand diesters), such as 2, 3, or 4-cyciohexenylacrylate, bicyclo (2,2,1) hept-5-ene-2-yl esters of acrylic acid,methacrylic acid, maleic acid (monoor diesters), fumaric acid (mono anddiesters) and itaconic acid (monoand diesters); vinyl ethers and vinylthioethers of cycloalkenols and cycloalkene thiols such as vinylcyclohex-4-ene-l-yl ether, vinyl ether of bicyclo (2,2,1)hept-5-ene-2-ol, vinyl esters of cycloalkene carboxylic acids such asvinyl cyclohex-3-ene-l-carboxylic acid or vinyl bicyclo (2,2,1hept-S-ene-2-carboxylate.

Among the effective graft-linking monomers, allyl group containingcompounds are preferred, particularly allyl esters of ethylenicallyunsaturated acids. Most preferred are allyl acrylate, allylmethacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate,allyl acid maleate, allyl acid fumarate, and allyl acid itaconate.Another category of allyl compounds which are highly effective, but notso preferred as the foregoing materials, are the diallyl esters ofpolycarboxylic acids which do not contain polymerizable unsaturation.Where two or more allyl groups occur in a single compound, one will tendto polymerize with substantially greater ease than another.

The diene elastomers of the present invention include polybutadiene orsimilar compounds such as polyisoprene, polychloroprene and poly(cyanobutadiene). The diene may be copolymerized with or without othermonomers such as alkyl and aralkyl acrylates and methacrylates, otheracrylic monomers and other ethylenically unsaturated monomers as listedabove under acrylic elastomers. These elastomers may containcross-linking monomers and graft-linking monomers as listed above.Preferred are those elastomers which contain 50 to 100 parts by weightdiene, 0 to 50 parts by weight acrylic monomer, O to 50 parts otherethylenically unsaturated monomer, 0 to 2 parts cross-linking monomerand O to 1 parts graft-linking monomer. These elastomers may be preparedin bulk, in emulsion, or in solution, and again may be preparedsequentially with different combinations of the above monomers ordifferent concentrations of the above monomers. The elastomers may haveattached to them subsequent stages which may be considered rigid, chosenas to amount and composition so as to provide dispersibility andcompatibility with subsequent stages or with the polycarbonamide to bemodified or to prevent the penetration of monomer into the elastomer.These elastomers may contain transfer agents in either one or allphases.

The polyester-urethane elastomers are prepared from a diisocyanatecompound and one or more compounds containing active hydrogenfunctionality, one of which is a polyester. Examples ofpolyester-urethane elastomers include elastomers prepared byisocyanates, both of the aliphatic and aromatic types, a saturated orunsaturated polyester, preferably a hydroxyl-terminated polyester, andoptionally other active hydrogen-containing compounds including alkanediols, both saturated and unsaturated, hydroxyalkyl esters of acrylicand methacrylic acid, and the like. These elastomers are commonlyprepared in bulk or in solution.

Polyether-urethane elastomers may be used in this invention. Theseelastomers are similar to'the polyester-urethane elastomers except forthe inclusion of the polyether. Generally, hydroxyl-terminatedpolyethers are utilized along with other active hydrogen-containingcompounds, either saturated or unsaturated. Polyester elastomers mayalso be used in this invention. These polyesters are generally preparedfrom aliphatic diacids of either the saturated or unsaturated varietyand aliphatic diols. Acrylonitrile and methacrylic acid as well as othercompounds may be included for the maximum development of impactstrength.

Ethylene-propylene-diene rubbers which have been converted into aqueousemulsion by known techniques can also be used as elastomers.

The preferred elastomer content of the multiphase polymer is 50 to 90percent, most preferred is 60 to 80 percent.

The outer rigid phase is comprised of a rigid thermoplastic containing acopolymerizable acid.

The elastomer-containing amine-reactive moiety-containing polymer may beprepared by bulk, suspension, emulsion, or solution polymerizationprocedures. The polymers may be prepared in sequential stages underconditions to provide physical and/or chemical attachment between thestages. The stages may be of varying harness and may range from thesoftest elastomer to the hardest rigid phase to provide improvedhandling characteristics and processability. These intermediate stagesmay also serve as a barrier to the penetration of subsequent monomeradditions into the elastomer. The polymer may contain chain transferagents in either one or all of the phases.

The monomers used for the rigid thermoplastic portion include a majority(e.g., 50-99 percent) of alkyl methacrylate, styrene, a-methylstyrene,halostyrene, acrylonitrile, methacrylonitrile, and olefins whichpolymerize to give polymers having a heat distortion temperature greaterthan about C., preferably greater than 50 C. The rigid thermoplasticportion of this phase includes homopolymers or copolymers of alkylmethacrylates wherein the alkyl group contains one to 15, preferably oneto eight carbon atoms. The rigid thermoplastic phase may contain one ormore acrylic comonomers in quantities of 0 to 49 parts such as otheralkyl and aryl methacrylates, alkyl and aryl acrylates, alkyl and arylacrylamides, substituted alkyl and aryl methacrylates and acrylates suchas halogen, alkoxy, alkylthio. cyanoalkyl, amino, alkylthiol esters, andother substitutions, and may contain O to 40 parts of other unsaturatedmonomers including vinyl esters, vinyl ethers, vinyl amides, vinylketones, vinyl halides, vinylidene halides and olefins.

Typical of the monomers which may be used to prepare the hard phase areesters of acrylic and methacrylic acid such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, 2-ethylhexyl, stearyl, cyclohexyl,isobomyl, bornyl, fenchyl, norbornyl, adamantyl, benzyl, phenyl and thelike. Preferred are those alkyl esters of methacrylic and acrylic acidswherein the alkyl group contains one to four carbon atoms. The preferredcycloalkyl esters of methacrylic and acrylic acids have cycloalkylgroups containing four to 14 carbon atoms. The substituted esters ofmethacrylic acid and acrylic acid include chlorine and brominesubstituted lower alkyl esters; alkoxy substituted lower alkyl esterssuch as ethoxy and methoxy; alkylthio substituted lower alkyl esterssuch as ethylthio and methylthio; and cyanoalkyl substituted lower alkylesters such as cyanoethyl and the like. Styrene monomers includehalostyrenes, vinyl toluene, t-butyl styrene, a-methylstyrene, and thelike. Vinyl halides and vinylidene halides wherein halides includechloride, bromide, and fluoride; and olefins including ethylene,propylene, isobutylene and the like, can also be utilized.

The copolymerizable amine-reactive moiety-containing compounds used inthe outer rigid thermoplastic phase are those compounds containinggroups which can react with the amine groups in the polycarbonamide toform covalent bonds under the conditions of the blending describedbelow; such reactive groups include acids, anhydrides, epoxides,oxetanes, halides, isocyanates, isothiocyanates, etc. or groups whichconvert to amine reactive moieties under the blending conditions citedbelow. Preferably the amine-reactive moiety-containing compound is acarboxylic acid. Useful carboxylic acids include acrylic, methacrylic,itaconic, fumaric, maleic, citraconic, a-methylene glutaric, aconitic,methylene malonic, mesaconic acids and substituted acrylic acids such asahydroxymethylor a-halomethyl acrylic acids as well as acids such asmethacryloxy-propionic acid, acryloxyor methacryloxyisopropyl acidphthalate, acryloxyor methacryloxyethyl or isopropyl acid oxalate,maleate, suc' cinate, glutrate, and the like. The preferred acid contentin the interpolymer is l to 25 weight percent, most preferred is 5 to 10weight percent. Although the amine-reactive moiety-containing compound,e.g. the carboxylic acid compound, is preferably found in the outerrigid thermoplastic phase, it may be found in any of the stages of themultiphase polymer including the first elastomeric phase so long as thereactive groups are substantially free to react with the amines of thepolycarbonamide.

The composite interpolymers of the present invention are prepared bysuspension or emulsion polymerization procedures'utilizing a multistage,or sequential technique. In simplest form the elastomeric phase isformed in a first stage and the rigid thermoplastic phase is formed in asecond stage. Either the elastomeric or rigid phases can themselves alsobe sequentially polymerized. The monomers of the initial stage, togetherwith initiators, soap or emulsifier, polymerization modifiers and chaintransfer agents and the like are formed into the initial polymerizationmix and polymerized, e.g., by heating and mixing the emulsion, in wellknown and wholly conventional fashion, until the monomers aresubstantially depleted. Monomers of the second, and, in turn, of eachadditional stage are then added with appropriate other materials, e.g.,initiator, soap, and the like, so that the desired polymerization ofeach stage occurs in sequence to substantial exhaustion of the monomers.In each stage subsequent to the first, the amounts of initiator andsoap, if any, are maintained at a level such that polymerization occursat the surface of existing particles, and no substantial number of newparticles, or seeds" form in the emulsion. The stages can vary inhardness,

from a very soft elastomer first stage seed to the hardest rigidthermoplastic. Both the elastomer and the rigid thermoplastic cancontain transfer agents, in one or all stages, and any or all of thestages of the composite can contain polyfunctional crosslinkingmonomers.

When polymerizations are conducted in multi-stage, :equential processes,there can additionally be stages which are, in composition andproportions, a combination of the two distinct phases, and havingproperties which are intermediate there-between.

Polymerization is conducted in accordance with known techniques foreffecting emulsion or suspension polymerization, with the use ofconventional materials, including, for example, free-radical initiators,soaps and emulsifiers, modifiers of numerous types, and the like.

The polymerization reactions can be initiated by either thermal orredox-type initiator systems. Examples of thermal initiators include theorgano peroxides, such as benzoyl peroxide, substituted benzoylperoxides, acetyl peroxide, lauryl peroxide, t-butyl hydroperoxide,di-t-butyl peroxide; peresters, such as t-butyl peroxy-pivalate;azo-type initiators, such as azo-bis-isobutyronitrile; persulfates, suchas sodium, potassium, or ammonium persulfate; and peroxyphosphates, suchas sodium, potassium, or ammonium peroxyphosphate. Redox iniatorsinclude, for example, a combination of hydroperoxide, such as hydrogenperoxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and the like, and a reducing agent, such assodium, potassium or ammonium bisulfite, metabisulfite, or hydrosulfite,sulfur dioxide, hydrazine, ferrous salts, isoascorbic acid, sodiumformaldehyde sulfoxalate, and the like.

Examples of emulsifiers or soaps suited to the polymerization processesof the present invention include alkali metal and ammonium salts ofalkyl, aryl, alkaryl, and aralkyl sulfonates, sulfates, and polyethersulfates, fatty acids, ethoxylated fatty acids, esters, alcohols,amines, amides, alkyl phenols, complex organo-phosphoric acids and theiralkali metal and ammonium salts.

Chain transfer agents, including mercaptans, polymercaptans, andpolyhalogen compounds are often desirable in the polymerization mix.

Thus, the composite interpolymer of the present invention is comprisedof two discrete component phases chemically and/or physically linkedtogether. Because of the extreme complexity of the interrelations amongthe various ingredients, it is difficult and possibly meaningless torefer to the physical characteristics of the component phases. Becauseof the degree of crosslinking in the elastomer phase and theparticipation of residual unsaturation of the elastomer in thepolymerization of the rigid phase, no adequate or meaningfuldetermination of molecular weight can be ascertained. A portion of therigid phase is chemically bound to the elastomer; and an additionalportion is not. Extraction of the composite interpolymer permitsdetermination that the unattached portion of the rigid phase has ameasurable molecular weight, which varies with the amount of rigid phaseand the nature of the polymerization procedure, and which can ordinarilyvary from about 40,000 up to as much as 500,000 or even more. Theelastomer portion has been ascertained to generally have a swellingratio (weight of wet acetone extracted, insoluble gel/weight of dryacetone extracted gel) ranging from about 2 to 12, while theunextractable portion of the interpolymer as a whole has a swellingratio on the order of about 6 to 16.

Reference has heretofore been made to the polymerization of the rigidphase at or onto the surface of the elastomeric phase. When suchreferences occur herein, it should be understood that such terminologyis adopted for purposes of convenience and is believed to be notentirely descriptive of the results attained. While the phenomenainvolved are not so clearly understood that the following considerationsshould be considered binding, it does appear that the rigid phasemonomers penetrate and swell the elastomeric phase particles to someextent and are polymerized in the interior thereof.

Since such effects undersirably interfere with the impact properties,polymerization conditions are preferred which tend to minimizepenetration. The more rapid the polymerization of the rigid phasemonomers, the less time is available for penetration to occur.Accordingly, relatively large amounts of initiator, relatively hightemperatures, and relatively slow additions of the rigid phase monomersare preferred to minimize penetration. Even when such preferredconditions are observed, some penetration will still occur, but will notbe so large an element in determining the properties of the composite.it is theoretically desirable, as well, to insure that encapsulation ofthe elastomer phase by the rigid phase occurs; whether such an effect isin fact attained by observance of the preferred conditions has not beenascertained but the conditions are not inconsistent with such a result,at least where relatively large proportions of the rigid phase areemployed.

By control of the polymerization variables, it is possible to controlthe particle size of the elastomer in the fashion well known to the art.The particle size is not of narrow significance to the presentinvention, and can range from as low as about 500 A, or even less, up toas large as about 3,000 A or more.

The blend of the composite interpolymer and the polycarbonamide can beaccomplished by any known method. The blend can be prepared by mixingthe relatively dry coagulated or spray dried composite interpolymer withnylon chip or fiber flock and the resulting blend can be milled to forma well dispersed mixture in an extruder, a roll mill, or like equipmentwhereupon the blend can be extruded into sheet or shapes or can be blowninto film, can be spun into fiber, or can be granulated and used forinjection molding.

During the milling operation the heat used therein and/or producedthereby causes some of the carboxylic acid groups of the modifier toreact with some of the amine end groups of the polycarbonamide so thatcovalent carbonamide linkages form between the modifier and thepolycarbonamide. This reaction can conveniently be followed by thereduction in amine end groups as determined by titration such as withperchloric acid in phenol-methanol mixed solvent.

Another convenient method of blending the composite and the carbonamideis by mixing the composite latex dispersion or solution withpolycarbonamide fiber flock and milling to form a well dispersed mixturein a vacuum vented extruder or on a roll mill whereby the dispersingmedium or solvent is removed during the blending of the composite andthe polycarbonamide. The interpolymer latex dispersion or solution canalso be added to the polycarbonamide melt in an extruder with removal ofthe dispersing medium or solvent as liquid and/or vapor.

The preferred method is to blend composite latex solution or dispersionwith polycarbonamide flock of average length )4; k inch, said flockbeing prepared and having insufficient hot strength to be extrudableunder conditions normally used for thermoplastic resins; the latex-flockblend is passed through a vacuum vented extruder at elevated temperatureor is milled on a heated roll mill whereby the solvent or dispersingmedium, usually water, is removed during the blending of the compositeand the polycarbonamide. Alternatively coagulated, drum-dried, or spraydried modifier can be blended with the waste flock and extruded ormilled.

It is normal practice to include in such compositions compounds andmaterials which stabilize the products and inhibit oxidative, thermal,and ultraviolet light degradation. Such practices are contemplatedwithin the scope of the present invention, and appropriate stabilizersare ordinarily incorporated into the composite interpolymer and intoblends of the composite interpolymer with nylon. Stabilizers can beincluded at any stage from the polymerization process whereby thecomposite and/or the materials with which the composite is blended areformed to the final step of forming the final product. It is preferredthat stabilizers be included early in the life of such polymers topreclude the initiation of degradation before the material can beprotected. Accordingly, the

TABLE I-Continued EXAMPLE N0. 4 5 6 7 8 9 Polycarbonamide type 2 C C C CC Modifier level 7. 5 5. 7 4. 5 4. 5 2. 75 6.67 Second pass melttemperature, 284-286 279 282 282 95-297 Type of blend 3 Dry Wet Wet WetDry Dry Izod notched impact strength:

% bar, milled notch, 23 C. 2. 1. 9 2.0 2. (1

Do l. 1 l. 7 1. 1 1. 8

% bar, milled notch, 23 C .2. 4 2. J 3. 2 4. 2

M bar, milled notch, 0 C 1. 3 1. J 2. 5 1.2

% bar, milled notch, 40 C. 0. 6 l). 7 1. 0 1. 3

% bar, molded notch, 23 C 2. 1 2. 2 3. 2 3. 0

% bar, molded notch, 0 C. 1. 1 1. 7 2.1) 2. 1)

bar, molded notch, 40 (5. (1.7 0.1 1. 1 1.3 Tensilcirnpaet, 23 0., 11/1,ft.-lb./in.-. 121/133 100/96 152/13 151/120 DIUL, C. at

66p.S-i 181 177 1117 181i 85 psi 156 175 171 171 Rockwell hardness, Lscale 1'19. 5 14. 5 115. 5 110.5 Vicottcmp.,C.,10mils Tensile strength:

Percent elongatyicld (dry/wet). 3.11/ 3 1/ 3.4/- 3.4/--

Percent clong. at break. 8, 200/ 1), 300/- 1l,200/

Stress at yield (dry/wet), 1)

Stress at break, p.s.i

Modulus (dry/wet), p.s.i. X Water absorption, percent at 23C.:

day lweek 4.0 4.4 4.5 Amine content meg/kg 19 15 19 1 See the followingtable:

Ex. No. Modifier composition 1BA/S/BDA/ALMA/IMMA/AA=57/13/0.35/0.14//28/2 2,3,4BA/S/ETEMA/BDA/ALMA/IMMA/AA=5G.5/l3/0.50/0.35/0.14//25/5 5BA/S/BDA/ALMA/IMMA/MAA=57/13/0.35/0.14//23/7 6BA/S/ETEMA/BDA/DALM/MMA/MAA=56.5/13/0.50/0.35/0.14I/2l/9 7BA/S/BDA/ALMA/IMMA/MAA/ME=57/13/0.35/0.28//21/9/O.3 8BA/S/BDMA/ALAl/MMA/MAA=/9.5/0.5/0.35/0.14/]35/15 9BA/S/ETEMA/BDA/ALMA/lMMA/ALMAflS/AA=40/9.5/0.5/0.25/0.1U//20/0.l0//15/l52 See the following table:

Relative viscosity Amine Polycarbonin 98% content amide H 804 (meg./:g.)

A Nylon 6 2.37 58 B Nylon 6 2. 55 49 0 Nylon 6 2. 50

9 Type of blend: DrySpray dried modifier tumble blended with nylon chipsor granules; Wet-Modifier latex blended with fiber flock.

EXAMPLE 1o 1 To 1 168.6 parts of a commercial butadiene/styrene 71/29latex (Firestone latex FR-S2003) containing 59.9 percent solids is added1,300 parts of water, 14 parts of sodium lauryl sulfate, 045 part cumenehydroperoxide, 165 parts of a 5 percent aqueous solution of acetic acid,and 0.6 part of sodium formaldehyde sulfoxalate. A mixture of 250 partsof methyl .methacrylate, 50 parts of acrylic acid and 0.45 part cumenehydroperoxide is added to the latex during 2 hours, during which timethe temperature rises from 30 to 41 C. At the end of the addition of thesecond stage, the mixture is heated at C. for 2 hours to complete thepolymerization. The final emulsion contains 34.0 percent solids. To thisemulsion is added parts of the following emulsion which stabilizes thelatex against oxidation during spray drying:

2.o-di-tert-butyl-4-methylphenol Methyl methacrylate Sodium laurylsulfate Water 20.0 parts by weight 20.0 parts by weight 4.0 parts byweight 56.0 parts by weight The emulsion is then spray dried to give afree-flowing powder which can be blended with the polycarbonamide bytumble blending and double pass extrusion. The test samples areinjection molded. The test results are shown in Table 11.

EXAMPLES ll TO 16 butadiene-l,3 75

styrene 21.2

methyl methacrylate 3.8

A redox initiator system composed of cumene hydroperoxide and sodiumformaldehyde sulfoxalate is used. The resulting latex has a particlesize of about 900 A. To 10 parts of this latex are added parts of amonomer mixture having the above shown composition using the same redoxpair and with such an emulsifier concentration that essentially no newparticles are formed. The resultinglatex has a particle size of about1700 A. The rigid thennoplastic stage containing the unsaturatedcarboxylic acid is now added in such a way that no new particles areformed, here, too, the initiator system is the above-mentioned redoxpair. To the final latex is added the following emulsion whichstabilizes the latex against oxidation during spray drying:

20.0 parts by weight 20.0 parts by weight 4.0 parts by weight 56.0 partsby weight 2, 6-di-tert-butyl-4-methylphenol methyl methacrylate Sodiumlauryl sulfate Water preferred practice is to include stabilizers in thepolymerization process, if compatible therewith, or in the polymer latexresulting from the polymerization.

The oxidative and thermal stabilizers useful in the materials of thepresent invention include those used in addition polymers generally.They include, for example, hindered phenols, hydroquinones, phosphites,and varieties of substituted members of those groups and combinationsthereof.

The untraviolet light stabilizers can also be those used in additionpolymers generally. Examples of ultraviolet light stabilizers includevarious substituted resorcinols, salicylates, benzotriazoles,benzophenones, and the like.

Other inclusions in the materials of the present invention includelubricants, such as stearic acid, stearic alcohol,

eicosanol, and other known types; colorants, including organic dyes,such as anthraquinone red and the like, organic pigments and lakes, suchas phthalocyanine blue and the like; and inorganic pigments. such astitanium dioxide, cadmium sulfide, and the like, fillers and particulateextenders, such as carbon black, amorphous silica, asbestos, glassfibers, magnesium carbonate, and the like; plasticizers, such as dioctylphthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils,and the like.

While only a few of such materials have been specifically recited, it isnot intended to exclude others; the recitation is exemplary only, andeach category of additive is common and well known in the art, includingextremely large numbers of materials which are equally well suited forinclusion in the materials of the present invention.

Such inclusions in the materials of the present invention can be made atany stage of preparation, in accordance with techniques well known tothose of ordinary skill in the art, in proportions which are commonlyemployed. Such additional materials are not of particular significancein the present invention and form no part thereof.

To assist those skilled in the art in the practice of the presentinvention, the following modes of operation are set forth asillustrations, parts and percentages being by weight unless otherwisespecifically noted:

EXAMPLES l to 9 Acrylic elastomer-based interpolymer compositions areprepared in accordance with the following procedure:

An elastomer monomer charge is emulsified, using an alkali metal salt ofdodecylbenzene sulfonic acid as the emulsifier. About percent of themonomer charge is polymerized with an alkali metal persulfate atelevated temperature to form a seed." The remainder of the elastomermonomer charge, with the further inclusion of other monomers, asappropriate, is

then added and polymerized, substantially to completion, whilecontrolling the soap or emulsifier concentration to prevent theformation ofa significant number of new particles. The resultant polymeris retained in emulsion form and an increment of appropriate monomers ispolymerized onto the particles to form a subsequent stage of a rigidthermoplastic containing copolymerized acid. The composite interpolymer(representing the sequentially polymerized elastomer and rigidthermoplastic) is isolated from the emulsion by spray drying or theemulsion is used per se. The seed technique affords effective control ofthe particle size, but, of course, is necessary onlyto the preparationof relatively large size particles. For small particle sizes, a singlestage polymerization of the elastomer can be utilized. The composite isblended with an appropriate polycarbonamide by the method designated andis extruded at the melt temperature shown in the table. The extrudedstrands are chopped into granules and the granules are injection moldedinto test speciments.

Nine different compositions are prepared and tested in accordance withthe above procedure, and the results are reported in Table I. Theelastomers in the example all comprise a major amount of butyl acrylate,a minor, but still substantial proportion of styrene, and minor amountsof ethylthioethyl methacrylate and 1,3-butylene diacrylate orl,3-butylene dimethacrylate. In Table I, these are designated forconvenience, respectively, BA, S, ETEMA, BDA, and BDMA. Otherinclusions, and their respectively abbreviations appearing in the table,are allyl methacrylate (ALMA), allyl acrylate (ALA), diallyl maleate(DALM), methyl methacrylate (M- MA), acrylic acid (AA), methacrylic acid(MAA), and mercaptoethanol (ME). Another matter of convenience in thetable is in the representation of the percentages of the components inthe elastomer. The base components, i.e., BA, 5, ETEMA, MMA, and acidtotal parts by weight, and other inclusions are reported as a percentageby weight based on the foregoing components. In this manner, changes ofcomposition are readily observed. In addition, a convenient short handrepresentation of composition and proportions is utilized. All thecomponents of each phase are represented in the heading of thetabulation, separated by a single slash; com ponents of different phasesare separated by a double slash. All the modifier compositions areprepared by the seed technique, and conditions are controlled so that anaverage particle size of about 2,000A is attained.

All of the examples shown in Table I can be extruded into 10 mil or lesssheet and the sheet can be vacuum thermoformed at 420-450 F. and plugmolded when the specimens are heated for 3 minutes at 450 F. Theunmodified nylons can not be extruded into sheet under the sameconditions as they lack hot strength and drool at the die lip.

TABLE 1 EXAMPLE N0. 1 2 3 Polycarbonamidc typo 3 li B Modiiicr lcvcl 025 Second Pass mclt tcmpcrntnri, 275-282 Type of blend 1 W Dr; Izodnotched impact strcnttth:

bar, milled notch, 23 (1. H 1.1 2.2 DO p e e V 1 1 z V V t). (i l. G Mrbar, millcd notch, 23 (1 1.1 3. 7 %r" bar, milled notch, 0 C V. l). 01.7 Mi bar, milled notch, -40 C. 0. 4 0. 3 M3 bar, molded notch, 23(l 1. 0 1.4 %i" bar, molded notch, 0 C 0. 5 1. 4 %i" bur, molded notch,10 (J U. 3 0. 0 Tensile impact, 23C., 11/l,it.-lh./in. /103 221/68 DTUL,(3.11

66 p.s.i .7 101 85 p.s.i 264 p.s.i 00 50 Rockwell hardness, L scale" 09.5 78. 5 Vicat temp, 0.,10 mils 202 201 Tensile strength:

Pcrccnt clong. at ycild (dry/wet)" 1. 3M4 t. 2/3. 0 3. 0/33 4. 2 1.1/-3. 8/ Percent along. at break. 38. 2 103 0 Stress at yield (dry/wet),p.s. 11,300/7,200 7, ZOO/3,400 E), (300/4, 800 9,000/-- 0,700/- 'J,500/Stress at break, p.s.i I 10, 000 ,200 0, 000 Modulus (dry/wet), p.s.i X10- 1.1/2.7 3.1/1.5 1. 11/22 1.0/- .i.t)/ LB/ \Vntci' absorption,pcrccnt at 23 (7.:

day 0 1 week 5. 5 1. .2 4. 0 5. 0 Amino content, mom/kg -10 13 11 58 1355 EXAMPLE n EXAMPLE l8 T a comlmercial polybutadiene law Pellets fromExample N) are blow extruded into film; the (Firestone latex FR-S2004)containing 59.8 percent solids is Properties Show" Table added 1,500parts of water, 10 parts of solution of acetic acid, and 2.5 partssodium formaldehyde sulfoxalate and the mix- EXAMPLE l9 ture is heatedto 50 C. A mixture of 400 parts of styrene, 100 Pellets from Example 2are blow extruded into film and a parts of acrylic acid and 2.5 parts ofcumene hydroperoxide is portion of this film is uniaxially oriented onthe Getty line. The added to the latex over 3 hours during which timethe temproperties are shown in Table III. perature rises to 60.5 C. Theemulsion is then heated at 65C 10 for 2 hours to complete thepolymerization. The final emul- EXAMPLE sion contains 33.6 percentsolids. To this emulsion is added parts of the stabilizer emulsion usedin Example l0. The emulsion is blended with polycarbonamide flock in aProdex- Henschel mixer and the resulting mixture is fed to a vacuum- 15EXAMPLE 21 vented, twin-screw extruder whereupon it is reextrudedthrough the same extruder and the pellets are injection Pellets fromExample 10 are melt spun into 34 denier fiber molded to provide testsamples. The results are reported in having the properties shown inTable IV. Table II.

Pellets from Example 2 are melt spun into denier fiber having theproperties shown in Table IV.

, TABLE II Example N o. I 10 ll 12 13 Nylon type 2 A A A B C O CModifier level 0 15 10 0 7. 5 7. 5 Second pass melt temperature, C290300 282-286 285-288 278 Type of blend Dry Dry Dry Wet Izod notchedimpact steength:

X bar, milled notch, 23 C. }4 bar, molded notch, 23 C bar, milled notch,23 C bar, milled notch, 0 C bar, milled notch, -40 bar, molded notch, 23C bar, molded notch, 0 C bar, molded notch, 40 Tensile impact, 23 0.,it.-lb./in. 238/ DTUL, C. at-

.s.i 60 Rockwell hardness, L scale; 09 87 91. 5 Vicat temp., C., 10 milsV Tensile strength:

Percent elong. at yield (dry/wet) 4. 2/ 4. 5/ 3. 6/4. 6

Percent clung. at break 177 Stress at yield (dry/wot), p.s.i l) 11,BOO/7,10

Modulus (dry/wet), p.s.i. (l0- 413/ 3. 4/- 3. 5-4. 5/2. 0-3. 8 3. 7/Water absorption, percent at 23 (1.:

1 week Amino content: mcqJxo. blend 58 7 1 Son the following table:

Example number Modifier composition 2 Same as Table I. 3 Same as Table}TABLE 111 Performance of nylon fi/acrylic blends (films prepared by blowextrusion) Example number 18 19 Capran 77C Processing date blown film:

Die temp., F 430 435 Melt pressure at 115 r.p.m., p.s.i 2, 350 2200 bniaxlal orientation:

Roll temp., F 380 350 Extension ratlo 3. 1 4. 5 Film thickness, mils 4 51 1 0.3 Tensile data, 50% min.:

Strain:

Yield, percent:

MD 9 11 13 D 9 17 l0 l2 6 Break percent:

D 190 25 14 TD 270 230 80 20 Strain:

Yield, 10 p.s.i.:

TABLE 1II:oLim ed Performance of nylon fi/acrylio blends (films preparedby blow extrusion) Example number 18 19 Capran 77C Tear data (tornacross MD): T

ear resistance, 1b./rni1 1. 4 1.4 3.6 11 1. 4 Work to tear, ln -lb./mil0. 71 0. 78 0. 43 1. 6 0. 86 Tear propagation resistance, 1b./rnil 0. 140. 13 0. 23 0. 41 0. 17 v Work to propagate tea, in.-1b./rnil 0.26 0. 250. 47 0. 94 0. 30 Brittle point by impact, 0., (across MD) -35 35 35 3535 Dimensional stability, change after 30 min./

200 0., percent MD/TD 1/0 -2/0 10/+10 /0 0/2 Equilibrium WaterAbsorption:

50% RH/77 F./4 days. 2. 8 3. 0 2. 4 2. 4 90% RG/77 F./4 days 4. 6 5. 73. 3. 8 2. 6 Solvent resistance, 7 days immersion at RI:

Water, wt. increase, percent 6.7 6. 7 6. 6. 7 10 Motor oi], wt.increase, percenL. 1. 0 l. 1 2. 4. 7 44 Veg. oil, wt. increase,percent 1. 0 0. 4 2. 2. 7 17 0, gas transmission rate, emfl/IOO inJ/day/atm 0.6 1.0 2.9 5.8

Data badly scattered. Most of the values iell around 49% and 127%elongation at break. 2 Not oriented.

* Allied 1 mil film. Sample broke before yielding.

EXAMPLE 22 A polyester from 98 parts of maleic anhydride, 1,314 parts ofadipic acid, and 620 parts of ethylene glycol is prepared in refluxingxylene. The xylene solution of the polyester is cooled to 80 C. and amixture of 600 parts of styrene, 200 parts of acrylic acid, 4 partst-dodecyl mercaptan and 16 parts of Lupersol 11 (a 75% solution oft-butyl peroxypivalate in mineral spirits) are added. The solution isheated at 80-90 C. for a total of 6 hours with two increments of eightparts each of Lupersol 11 being added at 2 hour intervals. The resultingsolution is added to polycarbonamide flock of relative viscosity 2.50 in98 percent H SO, and of an amine content of 50 meq./kg., thepolycarbonamide being present in a devolatilizing extruder as the melt,to give a final blend containing 15 parts of polyester-styrene-acrylicacid modifier. This blend is extrudable and has impact strength greaterthan the nylon flock used to prepare it.

EXAMPLE 23 A polyether prepared from 120 parts of trimethylol propaneand 5800 parts of propylene oxide is reacted with 522 parts of toluenediisocyanate and the product is reacted with 432 parts of hydroxypropylmethacrylate. This methacrylated poly (ether-urethane) is dissolved in amixture of 3,000 parts of methyl methacrylate and 860 parts ofmethacrylic acid and the monomers are polymerized with free radicalcatalysts by known methods. The resulting polymer is granulated and pansof the granules are blended with 80 parts of the nylon flock used inExample 22; the blend is double pass extruded to give a material havinghigher impact strength than the nylon flock.

EXAMPLE 24 A mixture of 71.7 parts of a polyester from ethylene glycol,propylene glycol (ethylene glycol: propylene glycol 80:20) and adipicacid (hydroxyl terminated, molecular weight of approximately 2,000), 3.0parts of 1,3-butylene glycol, 1.3 parts of 1,4-butanediol, 0.02 parts of2,6-di-tert-butyl-4- methylphenol, 186.9 parts of ethyl acetate, 0.5part of Catalyst T-l2 (di-butyltin dilaurate, M & T Chemicals, Inc.) and24.1 parts of Hylene W (Du Pont, 4,4'bis (isocyanatoparts ofhydroxyethyl methacrylate are added and the temperature is kept at 50 C.until the mixture no longer contains reactive isocyanate groups. To thissolution is added a mixture of 40 parts of methyl methacrylate, 6 partsof methacrylic cyclohexyl) methane) are heated at 50 C. whereupon 6.6:

acid, 0.23 part t-dodecyl mercaptan, and 0.7 part of t-butylperoxypivalate. The mixture is heated at 75 C. for 3 hours, anadditional 0.35 part of t-butyl peroxypivalate being added 1.5 hoursafter reacing 75 C. The resulting solution of modifier is added to thesame polycarbonamide as used in Example 22, the polycarbonamide beingpresent in a devolatilizing extruder as the melt, to give a final blendcontaining 10 percent modifier. This blend is extrudable and gives anlzod notched impact strength of 2.0 ft. -lb./in. of notch (one-eighthinch bar at 23 C.) and a tensile modulus of 390,000 psi dry.

EXAMPLE 25 A latex composition:

butadienel ,3 styrene methyl methacrylate 75 parts by weight 21.2 partsby weight 3.8 parts by weight parts by weight 3.3 parts by weight 16.7parts by weight methyl methacrylate ethyl acrylate methacrylic acid insuch a way that no new particles are formed, using the same redox pairas is used in Examples 1 1-14. To the final latex is added sufficientstabilizer emulsion as described in Examples 1 l-l4 to give 2 percent2,6-di-tert-butyl-4-methyl phenol on elastomer. The emulsion is spraydried and the free-flowing powder is blended withpolyhexamethylene-adipamide, Zytel 101, to give a blend containing 25%modifier. The blend is double pass extruded. The lzod notched impactstrength is 2.4 ft. -lb./in. of notch at 23 C. as compared to 0.8 ft.-lb./in. of notch for a comparable sample of unmodified Zytel 101.

EXAMPLE 26 The modifier of Example 25 is blended with Zytel 101 to givea blend containing 30 percent modifier. The blend is double passextruded to give a material having a notched Izod impact strength of 4.7ft. -lb./in. of notch at 23 C.

Work to break Elongation initial (g. om./ at break modulus denierStlilness Example Denier Tenacity (percent) (g./d.) crn (g./d

4. 03 12. 4 26. 8 0. 50 0. 17 3. 33 16. 5 8. 6 0. 47 0. 087 Percentchange 67. 9 -54. 7 Example 21 34 Dry. 2.110 Ill. 2 17.6 0. 07 0. 21 W1!r 2. ill! .51. l 7. ll 0.01 0.07 Percent change. -50 ll3.0 Nylontl 70/17Dry. 3.82 14.9 26.7 0. 69 0. 25 Wet 3. 20 20. 7 8. 4 0. 72 0. 11 Percentchange- -68. 6 56. 0

What IS claimed is:

1. An impact resistant nitrogenous polymer of 2.5 to 30 weight percentof a multiphase carboxylic acid-containing polymer comprising v A. afirst phase polymerized from monomers comprising 50 to 99.9 parts byweight alkyl acrylate wherein the alkyl group contains one to carbonatoms, butadiene or substituted butadiene; 0 to 40 parts by weight ofother ethylenically unsaturated monomers; 0 to 5 parts by weight of apolyethylenically unsaturated crosslinking monomer; and0 to 5 parts byweight of a graft-linking monomer; and I I a final rigid phasethermoplastic stage containing aminereactive carboxylic acid groups andpolymerized from monomers comprising 1 to 50 parts by weight of acopolymerizable carboxylic acid, 50 to 99 parts by weight of amemberselected from the group consisting of alkyl methacrylates,styrenes, acrylonitrile, methacrylonitrile and olefins thatwhenhomopolymerized, form polymers having a heat distortion temperaturegreater than about C.; 0 to 49 parts by weight of another acrylicmonomer; and 0 to 40 parts of another copolymerizable ethylenicallyunsaturated monomer. said multiphase carboxylic acid-containing polymergrafted to the terminal amine groups of a polycarbonamide containingrecurring amide linkages as an integral part of the polymer chain, saidgrafting by reaction of an acid group of the multiphase polymer with anamine end group of the polycarbonamide.

2. The polymer of claim 1 wherein the multiphase polymer contains 50 to90 weight percent of the first phase.

3. The polymer of claim 1 wherein the multiphase polymer contains 60 to80 weight percent of the first phase.

4. The polymer of claim 1 wherein the first phase (A) of the multiphasepolymer is polymerized from monomers comprising 50 to 90 parts by weightalkyl acrylate wherein the alkyl group contains one to eight carbonatoms; 0 to'20 parts by weight other acrylic monomers; 5 to 20 parts byweight other ethylenically unsaturated monomers, 0.1 to 1.0 part byweight of a polyethylenically unsaturated crosslinking monomer, and 0 to1.0 part by weight of a graft-linking monomer.

5. The polymer of claim 1 wherein the alkyl acrylate of said multiphasepolymer is butyl acrylate.

6. The polymer of claim 1 wherein the copolymerizable carboxylic acid ofsaid multiphase polymer is acrylic acid.

7. The polymer of claim 1 wherein the copolymerizable carboxylic acid ofsaid multiphase polymer is methacrylic acid.

8. A process for making a modified polycarbonamide comprising (A)forminga first elastomeric phase by polymerization of a monomer chargeof 50 to 99.9 parts by weight alkyl acrylate wherein the alkyl groupcontains one to 15 carbon atoms, butadiene or substituted butadiene; 0to 40 parts by weight of other ethylenically unsaturated monomers; 0 to5 parts by weight of a polyethylenically unsaturated crosslinkingmonomer; and 0 to 5 parts by weight of a graft-linking monomer; and Step(B) comprises polymerizing in the presence of a product containing theelastomeric phase formed in (A), a monomer charge, comprising 10 to 50percent by weight of a final rigid phase thermoplastic stage containingcopolymerizable carboxylic acid groups and polymerized from monomerscomprising 1 to 50 parts by weight of a copolymerizable carboxylic acid;50 to 100 parts by weight of a member selected from the group consistingof alkyl methacrylates, styrenes, acrylonitrile, methacrylonitrile andolei'tns that, when homopolymerized, form polymers having a heatdistortion temperature greater than about 20 C.; 0 to 50 parts by weightof another acrylic monomer; and 0 to 40 pans of another copolymerizableethylenically unsaturated monomer.

B. forming an amine-reactive moiety-containing final rigid thermoplasticphase in the presence of a product containing the first elastomericphase; and

C. reacting a reactive moiety of 2.5 to 30 weight percent of theinterpolymer formed in (A) and (B) with an amine end group of apolycarbonamide polymer containing recurring amide linkages as anintegral part of the polymer chain to form a modifiedinterpolymer-polycarbonamide of improved impact strength.

9. The process of claim 8 wherein the first phase (A) is polymerizedfrom monomers comprising 50 to parts by weight alkyl acrylate whereinthe alkyl group contains one to eight carbon atoms; 0 to 20 parts byweight other acrylic monomers; 5 to 20 parts by weight otherethylenically unsaturated monomers; 0.1 to 1.0 part by weight of apolyethylenically unsaturated crosslinking monomer; and 0.1 to 1.0 partby weight of a graft-linking monomer.

10. The process of claim 9 wherein said alkyl acrylate is butylacrylate.

11. The process of claim 9 wherein said copolymerizable carboxylic acidis acrylic acid.

12. The process of claim 9 wherein said copolymerizable carboxylic acidis methacrylic acid.

UNHHED STATES PATENT ormtt CE'ITWECATE (W CU RECEWN Patent No. 3 668 27Dated n a 197;)

Inventor s Frederick; H. Owens and James S. Clovis It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

In the abstract, line 25, "resistance" should. read --resistant--.Column 1, line 22, "resent" should read. --present--; line 32, "affect"should read ---effect--; line 6 "grater" should read. --greater--.Column 2, line 416, "diamine" should read. --diaminesline 60, OH should.read. 6; lll g line 71 after "Xylene" insert -C-N- C-N- Column 3, line19 "elastomer" should read elastomers--; line 69,

"unsatu-rated" should read --unsaturated--. Column LP, line 29'subsequenly" should read. -subsequentlye-;' line 3.1 "additional"should. read. --ad.dition--; line as, "o-allyl" should. read --o- Ially-l-; line #6, "o-allkyl should read. --O-alkyl-'; line 50,

V "math-acrylic" should read -methacrylic-. Column 5, line 56, "harness"should. read. -'-hard.ness---. Column 6, line +5, "glutrate" I should.read --glutarate'--. Column 9, line 9, "untraviolet" should read--ultraviolet-- Column 10, line 12, 'onl to" should. read. --only to".In Table I, "Do" should read --l/ bar, molded.

' notch, 23C"; "Tensile impact, 23C ll/l ft. -lb./in.' should.

read. --Tensile impact, 23C. machine direction/transverse direction, ft.lb./in.- "yeild" should read --yield.--; adjacent "Amine contentmeg./kg." under "Example 9" should appear --l3--;

footnote 1-, Example No. .6 after "BALM", shouldreadfootnote 2"Aminecontent (meg./g. should read .--Amine content (meg./kg. Column 12,line 56, after. "formed" delete insert Column 13, line 5, after "of"second occurrence,

insert --a 5% aqueous--; in Table II, after "Tensile impact, 23C.

ft.-.lb../in. insert --(machine direction/transverse direction)";

adjacent "Modulus" under "ll", "3. 5- 5/2.0-3.8" should read --3. 5-5/2.'O-3.0--; "Amine content; meq./Xo. blend" should. read --Aminecontent; me :i./l :g.-.- In Table III, under "Equilibrium waterAdsorption", "90% RG" should read "90% RH-.-'. Column 17,

line "0 change to Column 18,, line 39, change to line #0, eliminate"13.".

Signed and sealed this 3rd day of July 1973.

Attestz- I EDWARD M.FLETCHE-R,J'R. Rene Tegtmeyer Att'esting OfficervActing Commissioner of Patents FORM FO-1050 (10-69) uscoMM-oc sows-ps9 vR 1.1.5. GOVERNMENT PRINTING OFYFICE I 1959 035G-334

2. The polymer of claim 1 wherein the multiphase polymer contains 50 to90 weight percent of the first phase.
 3. The polymer of claim 1 whereinthe multiphase polymer contains 60 to 80 weight percent of the firstphase.
 4. The polymer of claim 1 wherein the first phase (A) of themultiphase polymer is polymerized from monomers comprising 50 to 90parts by weight alkyl acrylate wherein the alkyl group contains one toeight carbon atoms; 0 to 20 parts by weight other acrylic monomers; 5 to20 parts by weight other ethylenically unsaturated monomers, 0.1 to 1.0part by weight of a polyethylenically unsaturated crosslinking monomer,and 0 to 1.0 part by weight of a graft-linking monomer.
 5. The polymerof claim 1 wherein the alkyl acrylate of said multiphase polymer isbutyl acrylate.
 6. The polymer of claim 1 wherein the copolymerizablecarboxylic acid of said multiphase polymer is acrylic acid.
 7. Thepolymer of claim 1 wherein the copolymerizable carboxylic acid of saidmultiphase polymer is methacrylic acid.
 8. A process for making amodified polycarbonamide comprising (A) forming a first elastomericphase by polymerization of a monomer charge of 50 to 99.9 parts byweight alkyl acrylate wherein the alkyl group contains one to 15 carbonatoms, butadiene or substituted butadiene; 0 to 40 parts by weight ofother ethylenically unsaturated monomers; 0 to 5 parts by weight of apolyethylenically unsaturated crosslinking monomer; and 0 to 5 parts byweight of a graft-linking monomer; and Step (B) comprises polymerizingin the presence of a product containing the elastomeric phase formed in(A), a monomer charge comprising 10 to 50 percent by weight of a finalrigid phase thermoplastic stage containing copolymerizable carboxylicacid groups and polymerized from monomers comprising 1 to 50 parts byweight of a copolymerizable carboxylic acid; 50 to 100 parts by weightof a member selected from the group consisting of alkyl methacrylates,styrenes, acrylonitrile, methacrylonitrile and olefins that, whenhomopolymerized, form polymers having a heat distortion temperaturegreater than about 20* C.; 0 to 50 parts by weight of another acrylicmonomer; and 0 to 40 parts of another copolymerizable ethylenicallyunsaturated monomer. B. forming an amine-reactive moiety-containingfinal rigid thermoplastic phase in the presence of a product containingthe first elastomeric phase; and C. reacting a reactive moiety of 2.5 to30 weight percent of the interpolymer formed in (A) and (B) with anamine end group of a polycarbonamide polymer containing recurring amidelinkages as an integral part of the polymer chain to form a modifiedinterpolymer-polycarbonamide of improved impact strength.
 9. The processof claim 8 wherein the first phase (A) is polymerized from monomerscomprising 50 to 90 parts by weight alkyl acrylate wherein the alkylgroup contains one to eight carbon atoms; 0 to 20 parts by weight otheracrylic monomers; 5 to 20 parts by weight other ethylenicallyunsaturated monomers; 0.1 to 1.0 part by weight of a polyethylenicallyunsaturated crosslinking monomer; and 0.1 to 1.0 part by weight of agraft-linking monomer.
 10. The process of claim 9 wherein said alkylacrylate is butyl acrylate.
 11. The process of claim 9 wherein saidcopolymerizable carboxylic acid is acrylic acid.
 12. The process ofclaim 9 wherein said copolymerizable carboxylic acid is methacrylicacid.